The invention relates to a process for the preparation of polybutadienes with a reduced solution viscosity/Mooney viscosity ratio using functional dienes, the polybutadienes which can be prepared in this process, the use of the polybutadienes according to the present invention for the preparation of rubber mixtures, the use of the rubber mixtures for the production of all types of shaped articles, and the compound dimethyldi-2,4-pentadienyl-(E,E)-silane as an intermediate product for the preparation of the polybutadienes according to the present invention.
Polybutadiene with a high content of cis-1,4 units has been produced on a large industrial scale for a relatively long time and is employed for the production of tires and other rubber goods and for impact modification of polystyrene.
Catalysts based on compounds of the rare earths, as described in EP-A1-0 011 184 and EP-A1-0 007 027, are currently almost exclusively employed to achieve high contents of cis-1,4 units.
However, in addition to the many industrial advantages, the commercially available polybutadienes with high contents of cis-1,4 units, particularly polybutadienes prepared with catalysts based on the rare earths, have the disadvantage that they have a relatively high solution viscosity with respect to the Mooney viscosity. This is a disadvantage in the preparation and processing of the polybutadienes and for the use of these polybutadienes as impact modifiers for thermoplastics.
Thus, an object of the present invention is to provide polybutadienes with better processability. Another object was to provide polybutadienes which offer advantages when employed as impact modifiers for thermoplastics.
This object is achieved according to the present invention by a process for the polymerization of dienes, characterized in that polydienyl compounds are employed as comonomers.
Polydienyl compounds in the context of the present invention are condensation products of dienes of the general formula
Rz-yxe2x80x94Xxe2x80x94(xe2x80x94CR2xe2x80x94CRxe2x95x90CRxe2x80x94CRxe2x95x90CR)yxe2x80x83xe2x80x83(I)
wherein
R in each case independently of one another, represents a radical chosen from the group of H, C1-C20-alkyl, C6-C20-aryl and C7-C20-alkylaryl, which in its turn can be mono- or polyunsaturated or saturated,
X represents an element from the group consisting of C, Si, Ge, Sn, B, Al, N, P, O and S, preferably C or Si, or X
xe2x80x83represents a polysubstituted alkyl or aryl link, such as xe2x80x94(CR2)nxe2x80x94, xe2x80x94Oxe2x80x94(CR2)nxe2x80x94Oxe2x80x94, xe2x80x94C6R4xe2x80x94 or xe2x80x94O-aryl-Oxe2x80x94,
xe2x80x83wherein
z represents the number of substituents necessary to satisfy the valencies of X
R has the same meaning as above, and
y represents an integer greater than 2 and is not greater than z, and preferably y=2.
Preferred polydienyl compounds are dimethyldi-2,4-pentadienylsilane, methyltri-2,4-pentadienylsilane and tetra-2,4-pentadienylsilane.
Polydienyl compounds can be prepared by techniques known to one of ordinary skill in the art.
A preferred polydienyl compound, dimethyldi-2,4-pentadienyl-(E,E)-silane, can advantageously be prepared from a technical-grade mixture comprising 1,3-pentadiene by reaction with butyllithium/potassium tert-butylate, coupling with dimethyl-dichlorosilane and subsequent distillation (cf. example 1). The invention also provides dimethyldi-2,4-pentadienyl-(E,E)-silane as an intermediate product.
It is common that various polydienyl compounds can also be employed as a mixture.
The molar ratio of the polydienyl compounds to the conventional dienes is as a rule in the range from 1:10 to 1:20,000, preferably 1:50 to 1:10,000, and most preferably, 1:100 to 1:5,000.
Conventional dienes in the context of the present invention are all the dienes which are known to one of ordinary skill in the art and have been employed with respect to polybutadiene, in particular 1,3-butadiene, 1,2-butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene.
Suitable catalysts for the polymerization of the dienes and polydienyl compounds are preferably the catalyst systems which are known to one of ordinary skill in the art and are based on the rare earths, comprising
A) an alcoholate of the rare earths (II),
a carboxylate of the rare earths (III),
a complex compound of the rare earths with diketones (IV) and/or an addition compound of the halides of the rare earths with an oxygen or nitrogen donor compound (V), of the following formulae: 
xe2x80x83and MX3 m donor (V),
B) an aluminum-trialkyl, a dialkylaluminum hydride and/or an alumoxane of the formulae (VI) to (IX):
AlR3xe2x80x83xe2x80x83(VI)
HAlR2xe2x80x83xe2x80x83(VII),
xe2x80x83wherein, in the formulae xe2x80x83(Alxe2x80x94O)n+1xe2x80x83xe2x80x83(IX)
and
M denotes a trivalent element of the rare earths with atomic numbers 57 to 71,
R is identical or different and denotes alkyl radicals having 1 to 10 carbon atoms,
X represents chlorine, bromine or iodine,
m denotes 1 to 6 and
n denotes 1 to 50,
C) and at least one further Lewis acid.
Preferred compounds A) are those in which M denotes lanthanum, cerium, praseodymium or neodymium or a mixture of elements of the rare earths which comprises at least one of the elements lanthanum, cerium, praseodymium or neodymium to the extent of at least 10 wt. %.
Compounds A) in which M denotes lanthanum or neodymium or a mixture of rare earths which comprises lanthanum or neodymium to the extent of at least 30 wt. % are most preferred.
Examples of suitable carboxylates of the rare earths are: lanthanum tris-(2,2-diethyl-hexanoate), praseodymium tris(2,2-diethyl-hexanoate), neodymium tris(2,2-diethyl-hexanoate), lanthanum tris(2,2-diethyl-heptanoate), praseodymium tris(2,2-diethyl-heptanoate), neodymium tris(2,2-diethyl-heptanoate), lanthanum versaticate (lanthanum salt of Versatic Acid, commercial product of Shell Chemie), praseodymium versaticate and neodymium versaticate, lanthanum naphthenate, praseodymium naphthenate and neodymium naphthenate.
Examples of suitable aluminumalkyls B) are: trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, di-n-butylaluminum hydride and di-iso-butylaluminum hydride. Triethylaluminum, triisobutylaluminum and diisobutylaluminum hydride are preferred.
Lewis acids are employed as component C. Examples, which may be mentioned, are the organometallic halides in which the metal atom belongs to group 2 or 13, 14 or 15 of the periodic table according to IUPAC 1985 and halides of elements of group 15 of the period table according to IUPAC 1985, such as methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, 1-methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride and tin tetrachloride.
Diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide and ethylaluminum dibromide are preferred.
The reaction products of alkylaluminum compounds with halogens, e.g., triethylaluminum and bromine, as well as alkyl halides, aryl halides, arylalkyl halides and chlorosilanes, can also be employed as component C.
The molar ratio in which the catalyst components are used can be varied within wide limits.
The molar ratio of component A to component B is 1:1 to 1:100, preferably 1:3 to 1:80, and most preferably 1:3 to 1:50. The molar ratio of component A to component C is 1:0.4 to 1:15, preferably 1:0.5 to 1:8.
The polymerization is carried out in organic solvents. These solvents must be inert towards the catalyst system used. Suitable solvents are e.g. aromatic, aliphatic and cycloaliphatic hydrocarbons, such as benzene, toluene, pentane, n-hexane, iso-hexane, heptane and cyclohexane.
The polymerization can be carried out both continuously and discontinuously.
The polymerization is carried out at a temperature between xe2x88x9220 and 150xc2x0 C., preferably between 0 and 120xc2x0 C.
In a conventional embodiment, components A, B and C are added to a mixture of 100 parts by wt. of solvent with 5 to 50 parts by wt., preferably 8 to 30 parts by wt. of monomer.
When the desired conversion has been reached, the catalyst is deactivated by addition of small amounts of, for example, water, carboxylic acids or alcohols.
Conventional stabilizers can be added to the polymer solution in conventional amounts before working up. Stabilizers which are used are e.g. sterically hindered phenols or aromatic amines or phosphites, such as e.g. 2,6-di-tert-butyl-4,5-methyl-phenol.
The polymers are isolated by evaporation of the polymer solution, by precipitation with a non-solvent, such as, for example, methanol, ethanol or acetone, or, preferably, by steam distillation of the solvent.
After stripping with steam, the water is removed with suitable sieve or screw units, such as expeller or expander screws, or a fluidized bed dryer.
Drying is carried out by conventional processes, e.g. in a drying cabinet or in a screw dryer.
When the polydienyl compounds according to the present invention are employed, an undesirable increase in the Mooney viscosity may occur, but this can easily be compensated by an increased addition of B), particularly diisobutylaluminum hydride, or of A). The amount of additional B) needed depends on the required Mooney viscosity of the end product and can easily be determined by a few preliminary experiments.
It may furthermore be advantageous to preform the catalysts before use. In this case, the catalyst constituents A), B) and C) are mixed, with the addition of in the range from 1 part to 100 parts of diene per part of A), and the mixture is kept for several minutes to several days, optionally with occasional cooling to 10 to xe2x88x9280xc2x0 C., before the system is added to the polymerization solution.
Polybutadiene, particularly that prepared with catalysts of the rare earths, with a reduced ratio of solution viscosity (SV) to Mooney viscosity (MV), the cold flow simultaneously having low values with respect to the solution viscosity, has advantages in the preparation process and in transportation, storage and processing.
In the case of conventional Nd-polybutadiene, the ratio of solution viscosity (SV) to Mooney viscosity (MV) is usually in the range from 5 to 30. In the case of the polybutadienes according to the present invention, the ratio of solution viscosity (SV) to Mooney viscosity (MV) is in the range from 0.5 to 15.
The polybutadienes according to the present invention are, furthermore, suitable for impact modification of plastics.
The invention, therefore, also provides the polybutadienes which can be prepared in the process according to the present invention.
The polybutadienes according to the present invention can be used by themselves, as a blend with aromatic or aliphatic oils or as a mixture with other rubbers. Synthetic rubbers are also suitable, in addition to natural rubbers, as additional rubbers for the production of rubber vulcanization products. Preferred synthetic rubbers are described, for example, by W. Hofmann, Kautschuktechnologie [Rubber Technology], Gentner Verlag, Stuttgart 1980 and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989. They include, inter alia,
The invention also provides the rubber mixtures, which as a rule comprise 5 to 300 parts by wt. of an active or inactive filler, such as e.g.
The fillers mentioned can be employed by alone or as a mixture. In a most preferred embodiment, the rubber mixtures comprise as fillers a mixture of light-colored fillers, such as highly dispersed silicas, and carbon blacks, the mixing ratio of light-colored fillers to carbon blacks being 0.05 to 20, preferably 0.1 to 10.
The fillers are preferably added to the solution of the polybutadiene or polybutadienes according to the present invention as solids or as a suspension in water or a solvent. The rubber solution can be prepared beforehand, but the solution originating from the polymerization is preferably employed directly. The solvent is then removed by means of heat or, preferably, with the aid of steam. The conditions of this stripping process can easily be determined by preliminary experiments.
Furthermore, the fillers are preferably added to the solid polybutadiene according to the present invention or a mixture of rubbers and are mixed into this in a known manner, e.g. with a kneader.
The rubber mixtures according to the present invention, optionally, furthermore comprise crosslinking agents. Crosslinking agents which can be employed are sulfur or peroxides, sulfur being most preferred. The rubber mixtures according to the present invention can comprise further rubber auxiliary products, such as reaction accelerators, antiaging agents, heat stabilizers, light stabilizers, anti-ozone agents, processing auxiliaries, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, retardants, metal oxides and activators, such as triethanolamine, polyethylene glycol, hexanetriol etc. which are known to the rubber industry.
In the preferred rubber mixtures with highly active precipitated silicas, the use of additional filler activators is particularly advantageous. Preferred filler activators are sulfur-containing silyl ethers, particularly bis-(trialkoxysilyl-alkyl) polysulfides, as described in DE-A-2.141.159 and DE-A-2.225.577, oligomeric and/or polymeric sulfur-containing silyl ethers of DE-A-4.435.311 and EP-A-0 670 347, mercaptoalkyltrialkoxysilanes, preferably mercaptopropyltriethoxysilane, and thiocyanatoalkyl-silyl ethers, as described e.g. in DE-A-195 44 469.
The rubber auxiliaries are employed in conventional amounts, which depend, inter alia, on the intended use. Conventional amounts are e.g. amounts of 0.1 to 50 wt. %, based on the rubber.
Further mixing of the rubbers with the other rubber auxiliary products, crosslinking agents and accelerators mentioned can be carried out in a conventional manner with the aid of suitable mixing units, such as mills, internal mixers and mixing extruders.
Compounding and vulcanization are described in more detail, for example, in Encyclopedia of Polymer Science and Engineering, vol.4, p. 66 et seq. (compounding) and vol. 17, p. 666 et seq. (vulcanization).
The vulcanization of the rubber mixtures according to the present invention can be carried out at conventional temperatures of 100 to 200xc2x0 C., preferably 130 to 180xc2x0 C. (optionally under a pressure of 10 to 200 bar).
The rubber mixtures according to the present invention are outstandingly suitable for the production of all types of shaped articles.
Non-limiting examples of these shaped articles are O-rings, profiles, seals, membranes, tires, tire treads, damping elements and hoses.
Various tire components and tire treads are most preferred.
Furthermore, the rubber mixtures according to the present invention are suitable for impact modification of thermoplastics, particularly for polystyrene and styrene/acrylonitrile copolymers.